Synthesis of novel cobalt and iron complexes for sustainable catalytic hydrogenations

Aim of the present work of thesis is to synthesize new non-noble metal based complexes to be employ in redox reactions by a metal-ligand cooperative mechanism. The need of replacing toxic and expensive precious metal complexes with more available and benign metals, has led to the development of new compounds based on cobalt and iron, which are the metals investigated in this study. A carbonyl-tetrahydroborato-bis[(2-diisopropylphosphino)ethyl]amine-cobalt complex bearing a PNP-type ligand is synthesized by a three-step route. Optimization attempt of reaction route were assessed in order to lowering reaction times and solvent waste. New cobalt complex has been tested in esters hydrogenation as well as in acceptorless dehydrogenative coupling of ethanol. Other varieties of substrates were also tested in order to evaluate any possible applications. Concerning iron complex, dicarbonyl-(η4-3,4-bis(4-methoxyphenyl)-2,5-diphenylcyclopenta-2,4-dienone)(1,3-dimethyl-ilidene)iron is synthesized by a three steps route, involving transmetallation of a silver complex, derived from an imidazolium salt, to iron complex. In order to avoid solvent waste, optimization is assessed. Studies were performed to assess activity of triscarbonyl iron precursor toward imidazolium salt and silver complexes.

Dearomatizzazione organocatalitica regio- ed enantioselettiva di sali di piridinio attivati

In this work, we present the first regio- and enantioselective organocatalytic nucleophilic dearomatization of activated N-alkyl pyridinium salts. In particular, N-benzyl pyridinium bromides bearing electron-withdrawing substituents at the C3 position of the pyridine ring were chosen as substrates. These compounds were easily obtained through an alkylation reaction between benzyl bromides and the corresponding 3-substituted pyridines. Then, a wide range of nucleophiles and organocatalysts was tested, providing the best results when indole, a thiourea derived from quinidine and 1-benzyl-3-nitropyridinum bromide were employed as the nucleophile, the catalyst and the pyridinium salt, respectively. Subsequently, the reaction conditions were optimised evaluating different bases, solvents, N-benzylic protecting groups, molar concentrations and temperatures. With the optimized condition in hand, the scope of the reaction with different substituted indoles was explored, affording the corresponding 1,4-dihydropyridines in good yields, regio- and enantio-selectivities. In addition, several experiments were carried out in order to understand the mechanism of the reaction, showing an unusual pathway involving a covalently bound intermediate formed by addition of the catalyst to the pyridine unit.

Modular catalyst: from the tiling of a water plane to the design of a floating structure

La tesi nasce dalla volontà di agire sull’area della Darsena di Ravenna, strategica in quanto via d’acqua navigabile che congiunge il mare con il centro città ma dal potenziale ancora poco sfruttato. Il progetto è studiato per essere inserito come catalizzatore urbano, creando spazi di interazione attraverso elementi modulari galleggianti e riconfigurabili per adattarsi a programmi d’uso flessibili; tali elementi si aggregano formando un sistema che ristruttura lo spazio dell’attuale banchina, cambiandone la percezione da barriera a waterfront urbano. La necessità di ottenere una struttura con capacità di crescita e flessibilità programmatica sfocia in un approccio modulare seguendo il principio massima variazione/minimo numero di elementi i cui principi aggregativi si basano sulla tassellazione “Cairo”. Vengono studiate le possibilità di incorporare variazione ed eterogeneità all’interno del sistema senza comprometterne la modularità fino ad integrare percorsi multilivello. La definizione delle morfologie delle parti che compongono i moduli si basano sullo studio dei principi di galleggiamento, stabilità e yacht design: a partire dalla forma dello scafo adatta ai principi di tiling definiti in precedenza, tutte le parti che compongono le varie tipologie di modulo sono progettate cercando continuità e integrazione tettonica (geometrica, strutturale, funzionale e percettiva). Vengono proposte soluzioni integrate sia per le problematiche tipiche delle strutture galleggianti sia per l’inserimento di attività all’interno della soluzione architettonica. Vengono prototipati di una serie di moduli, scelti in modo da dimostrare i principi di ricombinazione, continuità, modularità e tiling.

Study of Co-based hydrotalcite-derived mixed metal oxides partially modified with silver as potential catalysts for N2O decomposition

Co-Al-Ox mixed metal oxides partially modified with Cu or Mg, as well as Ag were successfully prepared, characterized and evaluated as potential catalysts for the N2O decomposition. The materials were characterized by the following techniques: X-Ray Diffraction, Thermogravimetric Analysis (TGA), N2 Physisorption, Hydrogen Temperature-Programmed Reduction (H2-TPR), and X-ray photoelectron spectroscopy (XPS). Ag-modified HT-derived mixed oxides showed enhanced activity compared to the undoped materials, the optimum composition was found for (1 wt.% Ag)CHT-Co3Al. The catalyst characterization studies suggested that the improved catalytic activity of Ag-promoted catalysts were mainly because of the altered redox properties of the materials.

Bidentate N-heterocyclic carbene complex of Manganese as catalyst for hydrosilylation and hydroboration of double and triple bonds

Scopo del presente lavoro di tesi è la sintesi di un complesso di manganese contenente un legante bis N-eterociclico e la sua applicazione come catalizzatore nelle reazioni di idrosililazione e idroborazione di doppi e tripli legami. I composti organici sililati e borilati sono importanti prodotti intermedi in diversi settori della chimica fine grazie alla loro stabilità e alla loro capacità di essere ampiamente funzionalizzati. Idroborazione e idrosililazione, grazie allo sviluppo di catalizzatori appositi, permettono di ottenere questi composti riducendo coprodotti, sottoprodotti e condizioni operative estreme. Generalmente i catalizzatori impiegati industrialmente contengono metalli di transizione costosi, rari e non biocompatibili. Per questo motivo negli ultimi anni la ricerca si è concentrata sullo sviluppo di nuovi catalizzatori a base di metalli della prima serie di transizione tra cui il manganese, noto per essere abbondante sulla crosta terrestre, economico e biocompatibile. I composti N-eterociclici (NHC) sono una classe di leganti tra le più utilizzate poiché oltre a una grossa variabilità di caratteristiche steriche ed elettroniche, consentono di stabilizzare la specie metallica. I complessi N-eterociclici di manganese sono stati scarsamente applicati nelle reazioni di idroborazione e idrosililazione. Per questo motivo, il gruppo dove ho svolto il mio tirocinio si è dedicato a questo tipo di ricerca, sintetizzando e testando un complesso bis-NHC di manganese nell’idrosililazione di carbonili e solfossidi. Il mio lavoro si inserisce all’interno di questo ampio progetto, applicando nuovamente lo stesso complesso su una serie di substrati e reazioni differenti. In particolare, l’idrosililazione è stata applicata su alchini, alcheni e su carbonili (in questo caso attivando il complesso con la luce visibile). Inoltre, si è testata l’attività catalitica del complesso nell’idroborazione di alchini.

Theoretical and experimental investigations on homologation of ethanol to butanol using a ruthenium-based catalyst

The mechanism of homologation of bioethanol to butanol and higher alcohols via the Guerbet reaction was computationally and experimentally investigated. The catalytic pathway involves a ruthenium-based complex and a base co-catalyst which work simultaneously. Due to selectivity issues, secondary products were formed and high competition between main pathway and side reactions was recorded. Herein, the overall catalytic mechanism for all the processes involved in was investigated, also considering the principal side reactions, using density functional theory (DFT) methods and experiments to confirm theoretical outcomes. Due to the complexity of the reaction network, kinetic simulations were established from DFT results, confirming experimental products distribution and giving insights into the factors governing the reaction mechanism.

Development of a Predictive Control Function for a Plug-in Hybrid Electric Vehicle with Electrically-heated Catalyst

This master thesis work is focused on the development of a predictive EHC control function for a diesel plug-in hybrid electric vehicle equipped with a EURO 7 compliant exhaust aftertreatment system (EATS), with the purpose of showing the advantages provided by the implementation of a predictive control strategy with respect to a rule-based one. A preliminary step will be the definition of an accurate powertrain and EATS physical model, starting from already existing and validated applications. Then, a rule-based control strategy managing the torque split between the electric motor (EM) and the internal combustion engine (ICE) will be developed and calibrated, with the main target of limiting tailpipe NOx emission by taking into account EM and ICE operating conditions together with EATS conversion efficiency. The information available from vehicle connectivity will be used to reconstruct the future driving scenario, also referred to as electronic horizon (eHorizon), and in particular to predict ICE first start. Based on this knowledge, an EATS pre-heating phase can be planned to avoid low pollutant conversion efficiencies, thus preventing high NOx emission due to engine cold start. Consequently, the final NOx emission over the complete driving cycle will be strongly reduced, allowing to comply with the limits potentially set by the incoming EURO 7 regulation. Moreover, given the same NOx emission target, the gain achieved thanks to the implementation of an EHC predictive control function will allow to consider a simplified EATS layout, thus reducing the related manufacturing cost. The promising results achieved in terms of NOx emission reduction show the effectiveness of the application of a predictive control strategy focused on EATS thermal management and highlight the potential of a complete integration and parallel development of involved vehicle physical systems, control software and connectivity data management.